Gelatin hardening composition



United States Patent 3,305,376 GELATIN HARDENING COMPOSITION Donald M.Burness, Stanley W. (Iowan, and John A.

Ford, .lr., Rochester, N.Y., assignors to Eastman Kodak Company,Rochester, N.Y., a corporation of New .lersey No Drawing. Filed July 22,1963, Ser. No. 296,496

Claims. (Cl. 106-125) This invention relates to double ended organiccompounds, having terminal bromine atoms, as modifiers in gelatincompositions.

It is often desirable to provide addends to gelatin compositions whichserve in more than one capacity. Some compounds only act as hardeners,some as antifoggants in gelatin photographic emulsions and others assensitizers.

One object of our invention is to provide addends to gelatin which serveas both hardeners for gelatin and as antifoggants when incorporated inphotographic emulsions. Another object of our invention is to providedouble ended bromine compounds as useful gelatin hardeners. A furtherobject of our invention is to provide compositions of matter composed ofgelatin and double ended bromine compounds. Other objects of ourinvention will appear herein.

We have found that certain double ended bromine compounds for examplecertain bisurethans, bisureas, bisamides and urethan-ureas havingterminal =bromo atoms when incorporated in gelatin compositions exert ahardening effect thereon and when used in photographic emulsions serveas antifoggants. In adding these materials to gelatin compositions it isdesirable to use an amount suflicient to show a hardening effect whenthe gelatin composition is coated out in the form of layers. Althoughamounts as low as 0.1% based on the weight of the gelatin have shown ahardening effect in gelatin layers containing these compounds it ispreferable to incorporate 16% of the hardening compound (based on thegelatin) in the gelatin composition.

The gelatin hardeners which have been found to be effective inaccordance with the invention are as follows:

(1) Bisurethans of the following structure where X is selected from thegroup consisting of (CH n being 2-6,

BrCH CH CONHCOXCONHCOCH CH Br where X is selected from the groupconsisting of R R R R Where m=06 and R is selected from the groupconsisting of H and alkyls of 1-4 carbon atoms.

(3) Bisamides of the following structure BrCH CH CO--XCOCH CH Br where Xis selected from the same group as designated in (2).

(4) Urethan-ureas having the following structure *1 BrcHzcH CONHC OOXNCONHCO OHzOHzBr R being selected from the group of H and the alkylsof 14 carbon atoms, X is selected from the group of -(CH and and rt=24.

The compounds useful as hardeners in accordance with our invention aredouble ended type compounds in which the terminal portion of each endexhibit a 3-brornopropionyl structure. The 3-bromopropionyl compoundsuseful as addends to gelatin in accordance with our invention may beprepared by any convenient method. Some of these compounds areconveniently prepared by the simple acylation of an appropriate diaminewith 3-bromopropionyl chloride or bromide. In other cases, the desiredhardener may be conveniently prepared by reacting a 3-bromopropionylisocyanate with an appropriate compound such as a diamine, a dialcohol,an amino alcohol or the like. Johnson and Du blitz in J.A.C.S., 80, 3150(1958) refers to the reaction of the isocyanate with an alcohol and withan amine to form respectively an urethane (carbamate) and an urea.

The hardeners in accordance with our invention are useful for adding togelatin-silver halide photographic emulsions in that those compoundsexhibit a hardening action in the emulsion layers, have an antifogganteffect and in some cases may even act to increase the sensitivity of theemulsion. However, these addends are also useful in incorporating inother types of gelatin-coating compositions used for photographicpurposes such as subbing layers, overcoatings, antihalation layers andthe like, Where desirable to increase the resistance of the gelatinlayer against the effect of water particularly at an elevatedtemperature. These addends add to the resistance of the gelatin layer toswelling by water and increase the degree of temperature at which thegelatin layer disintegrates when immersed in water, the temperature ofwhich is gradually increased.

The following examples illustrate methods of preparing various compoundswhich are useful as addends to gelatin compositions in accordance withour invention.

Example 1 30.2 grams of 3-brornopropionyl chloride in solution in 50 ml.of ethylene chloride was added dropwise to a mixture of a solution of9.3 grams of hexamethylenediamine in 300 ml. of ethylene chloride and7.1 grams of sodium hydroxide in ml. of water at a temperaturemaintained at 1520. This reaction resulted in the formation of a solidwhich was filtered off and was washed consecutively with dilute HCl,dilute alkali and water and then dried. Recrystallization from ethanolyielded 24.6 grams of N,N'-bis 3-brornopropionyl hexamethylenediamine ascolorless crystals. This material had a melting point of 168.5470 C.

Example 2 The above procedure Was repeated except that the diamine usedwas ethylenediamine. N,N-bis(3-bromopropionyl)ethylenediamine wasobtained as a colorless product after recrystallization from methanol.This material had a melting point of l77.5178 C.

Example 3 The procedure described in Example 1 was repeated usingo-phenylenediamine as the diamine material. N,N'- bis(3-bromopropionyl)-o-phenylenediamine was obtained as a colorless solid having a meltingpoint of 189.5- 190" C.

Example 4 N,N-bis(3-bromopropionyl)piperazine having a melting point of103-104.5 C. was obtained.

Example A mixture of 350 ml. of dry chloroform, 35.6 grams ofN-bromosuccinimide, 2 ml. of allyl chloride and about 5 mg. of benzoylperoxide was refluxed together for 4 hours after which 4.3 grams ofethylene glycol was added to produce 25 grams of colorless solid whichwas recrystallized from methanol N,N dimethylformamide. The

1,15 dibromo-3,5,11,13-tetraoxo-6-oxa-4,10,12- triazapentadecane.

It is to be understood that the hardeners in accordance with theinvention may be employed in various photographic emulsions,photographic systems and in emulsions containing various chemicalsensitizers and addenda. Various types of emulsions and addenda whichmay be used in conjunction with these hardeners and processes in whichthese emulsions may be used are those referred to in US. Patent No.3,057,723, column 5, line 57 to column 8, line 27.

We claim:

1. A composition of matter comprising gelatin and a hardening amount ofcompound selected from the group consisting of the following:

A. Bisurethans having the structure BrCH CH CONHCOOXOCONI-ICOCH CH Brwherein X is selected from the group consisting of compound obtainedwhich melted at 192-1925 0., was ethylenebis 3-bromopropionylurethan). 0

Samples of the compounds prepared above were added to separate portionsof a sulfur and gold sensitized high- CH H I speed silverbromoiodide-gelatin photographic emulsion G (CI )T 0 (HC) which had beenpanchromatically sensitized with a CH cyanine dye. Each emulsion samplewas coated on a cellulose acetate film support at a coverage of 432 mg.of silver and 980 mg. of gelatin per square foot. Each 2 2 2 2- 2)2 2-2)2 sample was exposed on an Eastman 1B sensitometer, (c1-1 processedfor five minutes in Kodak DK-SO developer, fixed, washed and dried. Theresults obtained were as and follows: 2O 2 Cone., Rel. P The Addend Usedg./100 g. Speed Gamma Fog sgt li ir of Gel Water Control 100 1. 27 0.17990 Bis (3-1)romopropionyl)hexaincthylencdiaminm 3 100 1. 23 13 530 Do 6105 1.18 .14 470 B1s(3 b1 omopi opionyl)ethylcned1amn1o 3 83 1. 03 10350 D 6 80 1.15 .11 300 Contr 100 1. 18 .14 910Bis(3-bromopropionyl)-o-phenylencdianune 1 97 1. 33 13 610 Do 3 97 1.28.14 800 Control V 100 1. 20 .12 659 Bis(3-bro1noprop yl 1 91 1. 47 .10500 Do 5 1.40 .09 228 Control 100 1. 25 .13 676Ethylenebis(3-bromopropionylurethan) 1 74 1. 32 08 380 Other usefuladdends to photographic emulsions in :ac- B. Bisureas having thestructure cordance with our invention are the following:

(6) Tetramethylenebis 3-bromopropionyl-urethan) (BrcHzcHzcoNHco 2X (7)Hexamethylenebis(3-bromopropionylurethan) C. Bisamides having thestructure (8) Trans 1,4 cyclohexylened1methylb1s(3 bromo- (BrcH2cH2cO)2Xpropionylurethan) (9) 1,1,3,3tetramethylcyclobutane-2,4-diylbis(3-bromopropionylurethan) 10)2,2'-oxydiethylbis 3-bromopropionylurethan) (11) 2,2'-thiodiethylbis3-bromopropionylurethan) 12) 2,2-sulfonyldiethyl bis(3-bromopropionylurethan) 13) 3,6dithiaoctane-l,8-diylbis(3-bromopropionylurethan) (14) 6oxa-3,9-dithiaundecane-1,11-diylbis(3-bron1o-' wherein X in B and in Cis selected from the group consisting of D. Urethan-ureas having thestructure R BrCHzCHzOONHCOCXI ICONHCOCH2CH2Br wherein X is selected fromthe group consisting of and ( lHs and R is selected from the groupconsisting of H and alkyls of 14 carbon atoms.

2. A composition of matter comprising gelatin and a hardening amount ofa bisu-rethan having the structure (BrCH CH CONHCOO X wherein X isselected from the group consisting of (CH3): cn, C -orn *(OI-I2)2O(CI-I(CI-I92 3. A composition of matter comprising gelatin and a hardeningamount of a bisurea having the structure (BrCH CI-I CONHCO) X wherein Xis selected from the group consisting of and R being selected from thegroup consisting of H and alkyls of 1-4 carbon atoms.

4. A composition of matte-r comprising gelatin and a hardening amount ofa bisamide having the structure R being selected from the groupconsisting of H and alkyls of 1-4 carbon atoms.

5. A composition of matter comprising gelatin and a hardening amount ofa uret'han-urea having the structure wherein X is selected from thegroup of -(CH and and R is selected from the group of H and the alkylsof 14 carbon atoms.

6. A composition of matter comprising gelatin and a hardening amount ofN,N'-bis(3-bromopropionyl)hexamethylenediamine.

7. A composition of matter comprising gelatin and a hardening amount ofN,N-bis(3-bromopropionyl)ethylenediamine.

8. A composition of matter comprising gelatin and a hardening amount ofN,N'-bis(3-bnomopropionyl)phenylenediamine.

9. A composition of matter comprising gelatin and a hardening amount ofN,N'-bis(3-bromopropionyl)piperazlne.

10. A composition of matter comprising gelatin and a hardening amount ofethylene bis(3-bromopropionyl) urethan.

References Cited by the Examiner UNITED STATES PATENTS 12/1962 KnoX etal. 96lll 10/1963 Burness 96-111 NORMAN G. TORCHIN, Primary Examiner.

A. E. TANENHOLTZ, J. H. RAUBITSCHEK,

Assistant Examiners.

1. A COMPOSITION OF MATTER COMPRISING GELATIN AND A HARDENING AMOUNT OFCOMPOUND SELECTED FROM THE GROUP CONSISTING OF THE FOLLOWING: A.BISURETHANS HAVING THE STRUCTURE